U.S. patent application number 12/751411 was filed with the patent office on 2011-06-02 for method of increasing hydrophilic property of crystalline carbon using surface modifier and method of preparing platinum catalyst using the same.
This patent application is currently assigned to HYUNDAI MOTOR COMPANY. Invention is credited to Han Sung Kim, Ki Sub Lee, Hyung-Suk Oh, Bumwook Roh.
Application Number | 20110129762 12/751411 |
Document ID | / |
Family ID | 44069152 |
Filed Date | 2011-06-02 |
United States Patent
Application |
20110129762 |
Kind Code |
A1 |
Lee; Ki Sub ; et
al. |
June 2, 2011 |
METHOD OF INCREASING HYDROPHILIC PROPERTY OF CRYSTALLINE CARBON
USING SURFACE MODIFIER AND METHOD OF PREPARING PLATINUM CATALYST
USING THE SAME
Abstract
The present invention features a method for increasing
hydrophilic properties of crystalline carbon using a surface
modifier and a method for preparing a Pt/C catalyst using the same.
In certain preferred embodiments, the present invention features a
method for increasing hydrophilic properties of crystalline carbon
having water repellency by forming .pi.-.pi. interaction between
the surface of the crystalline carbon and a surface modifier and a
method for preparing a catalyst by supporting platinum (Pt) on the
crystalline carbon having increased hydrophilic property. The Pt/C
catalyst prepared by the methods of the present invention is useful
for the preparation of electrode materials for fuel cells.
Inventors: |
Lee; Ki Sub; (Seoul, KR)
; Roh; Bumwook; (Yongin, KR) ; Kim; Han Sung;
(Seoul, KR) ; Oh; Hyung-Suk; (Incheon,
KR) |
Assignee: |
HYUNDAI MOTOR COMPANY
Seoul
KR
KIA MOTORS CORPORATION
Seoul
KR
Industry-Academic Cooperation Foundation, Younsei
University
Seoul
KR
|
Family ID: |
44069152 |
Appl. No.: |
12/751411 |
Filed: |
March 31, 2010 |
Current U.S.
Class: |
429/524 ;
252/182.1; 502/185; 546/197; 548/307.1; 562/405; 562/457; 562/490;
568/67; 977/734; 977/742; 977/762 |
Current CPC
Class: |
B82Y 30/00 20130101;
C07D 235/28 20130101; C01B 32/174 20170801; D06M 2101/40 20130101;
H01M 4/92 20130101; H01M 4/926 20130101; C01B 32/18 20170801; H01M
8/1007 20160201; Y02E 60/50 20130101; C01B 32/05 20170801; B82Y
40/00 20130101; C07D 213/79 20130101; C07D 319/18 20130101; D06M
13/184 20130101; D06M 13/252 20130101; Y02P 70/50 20151101 |
Class at
Publication: |
429/524 ;
502/185; 252/182.1; 562/405; 562/490; 562/457; 546/197; 568/67;
548/307.1; 977/742; 977/734; 977/762 |
International
Class: |
H01M 4/583 20100101
H01M004/583; B01J 21/18 20060101 B01J021/18; H01M 4/90 20060101
H01M004/90; C07C 63/44 20060101 C07C063/44; C07C 63/36 20060101
C07C063/36; C07C 229/56 20060101 C07C229/56; C07D 211/06 20060101
C07D211/06; C07C 321/26 20060101 C07C321/26; C07D 235/28 20060101
C07D235/28 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 30, 2009 |
KR |
10-2009-0117213 |
Claims
1. A method for increasing the hydrophilic properties of
crystalline carbon using a surface modifier.
2. The method for increasing hydrophilic properties of crystalline
carbon according to claim 1, wherein .pi.-.pi. interaction is
formed between the surface modifier and the crystalline carbon and
hydrophilic property is provided by a hydrophilic functional group
of the surface modifier.
3. The method for increasing hydrophilic property of crystalline
carbon according to claim 1, wherein the surface modifier is one
selected from the group consisting of: 1-pyrenecarboxylic acid,
9-anthracenecarboxylic acid, fluorene-1-carboxylic acid,
1-pyrenebutyric acid, naphthoic acid, 1-pyreneacetic acid,
naphtho-2-aminopyridine-3-carboxylic acid,
1,4-benzodioxane-6-carboxylic acid, 2-mercaptobenzimidazole,
2-naphthalenethiol, 1-mercaptopyrene, 6-mercaptobenzopyrene and
1,4-benzenedithiol.
4. The method for increasing hydrophilic property of crystalline
carbon according to claim 1, wherein the crystalline carbon is one
selected from the group consisting of: carbon nanotube, carbon
nanofiber, carbon nanocoil and carbon nanocage.
5. A method for preparing a Pt/C catalyst, comprising: increasing
hydrophilic property of crystalline carbon using a surface
modifier; supporting platinum (Pt) on the crystalline carbon to
prepare a catalyst; and washing and drying thus prepared catalyst
to remove unwanted organic materials.
6. A Pt/C catalyst prepared by the method according to claim 5.
7. A fuel cell electrode comprising the catalyst according to claim
6.
8. A fuel cell comprising the electrode according to claim 7.
Description
CROSS-REFERENCE(S) TO RELATED APPLICATIONS
[0001] This application claims under 35 U.S.C. .sctn.119(a) the
benefit of Korean Patent Application No. 10-2009-0117213, filed on
Nov. 30, 2009, the entire contents of which are incorporated herein
by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates, generally, to a method for
increasing hydrophilic property of crystalline carbon using a
surface modifier and a method for preparing a platinum (Pt)/C
catalyst using the same. Preferably, the crystalline carbon having
increased hydrophilic property enables easier supporting of
platinum (Pt) and is preferably used in the preparation of fuel
cell electrode materials.
[0004] 2. Description of Related Art
[0005] A fuel cell, which transforms the chemical energy resulting
from the oxidation of the fuel directly into the electrical energy,
has been called the next-generation energy source. Particularly, in
the automobile-related fields, research has been directed to fuel
cells because of their advantages in improved fuel efficiency,
reduced emission, environmental friendliness, etc. In particular,
research has focused on catalysts for oxidation and reduction
reactions occurring in fuel cell electrodes.
[0006] In particular, research has been focused on the preparation
of platinum (Pt) into nanoparticles or to support well dispersed Pt
on carbon having high specific surface with high content in order
to suitably improve catalytic activity of fuel cells (J. Power
Sources, 139, 73). At present, carbon black is generally used as a
support for Pt, but its durability deteriorates because of
corrosion of carbon in the course of operation of the fuel cell (J.
Power Sources, 183, 619). Accordingly, research on fuel cell
catalysts using crystalline carbon with superior electrical and
physical properties, such as carbon nanotube (CNT), carbon
nanofiber (CNF) as a support have been actively carried out (J.
Power Sources, 158, 154).
[0007] However, CNT and CNF are difficult to apply for preparation
of a high-content, highly dispersed Pt/C catalyst since they tend
to agglomerate in a polar solvent because of surface water
repellency (Electrochim. Acta. 50, 791). Accordingly, functional
groups are attached after oxidizing the surface of carbon support
by means of plasma, air or strong acid. However, since plasma and
air may result in a strong oxidation enough to destroy the surface
structure of CNT or CNF, their application to a catalyst support
may lead to deterioration of durability (Adv. Mater., 7, 275).
Further, the acid treatment using strong acid such as nitric acid
or sulfuric acid (Chem. Eur. J., 8, 1151) may also lead to
destruction of the crystalline carbon structure and deterioration
of durability during the acid treatment procedure. Thus, its
application to a fuel cell catalyst support may result in increased
electrochemical corrosion.
[0008] A number of methods to increase hydrophilic property without
destruction of the surface structure of crystalline carbon have
been proposed (J. Mater. Chem., 18, 1977, J. Am. Chem. Soc. 123,
3838, Korean Patent Application Publication No. 2006-084785 US
Patent Application Publication No. 2004-115232 Korean Patent
Application Publication No. 2009-079935 and US Patent Application
Publication No. 2007-298168, all of which are incorporated by
reference in their entireties herein). These methods aim at
increasing hydrophilic property of the CNT surface using pyrene
compounds. In particular, an attempt to uniformly arrange Pt,
cadmium sulfide (CdS) and silica particles on CNT using
1-aminopyrene is disclosed in Adv. Funct. Mater. 16, 2431. Although
these methods are effective in improving hydrophilic property of
CNT, they are not suitably applicable to preparation of Pt/C
catalysts because water dispersibility decreases with time.
[0009] The above information disclosed in this the Background
section is only for enhancement of understanding of the background
of the invention and therefore it may contain information that does
not form the prior art that is already known in this country to a
person of ordinary skill in the art.
SUMMARY OF THE INVENTION
[0010] The present invention features a high-content, highly
dispersed Pt/C catalyst that is preferably prepared by suitably
increasing hydrophilic property of crystalline carbon by forming
noncovalent .pi.-.pi. interaction between a surface modifier and
the crystalline carbon and using the crystalline carbon as a
support of a fuel cell catalyst.
[0011] Accordingly, present invention preferably provides a method
for increasing hydrophilic property of crystalline carbon using a
surface modifier.
[0012] The present invention further provides a method for
preparing a catalyst by supporting platinum (Pt) on the crystalline
carbon with increased hydrophilic property.
[0013] In preferred embodiments, the present invention preferably
provides a method for suitably increasing hydrophilic property of
crystalline carbon using a surface modifier.
[0014] In other preferred embodiments, the present invention also
preferably provides a method for preparing a Pt/C catalyst,
including: increasing hydrophilic property of crystalline carbon
using a surface modifier; supporting Pt on the crystalline carbon
to suitably prepare a catalyst; and washing and drying thus
prepared catalyst to remove unwanted organic materials.
[0015] Preferably, the method for increasing hydrophilic property
of crystalline carbon using a surface modifier and the method for
preparing a Pt/C catalyst using the same according to the present
invention enable preparation of a high-content, highly dispersed,
highly durable Pt nanocatalyst wherein crystalline carbon has
suitably increased hydrophilic property by .pi.-.pi. interaction
between the crystalline carbon and the surface modifier and is
resistant to electrochemical corrosion. Preferably, the catalyst
may be usefully used, for example, as electrode material of fuel
cells.
[0016] It is understood that the term "vehicle" or "vehicular" or
other similar term as used herein is inclusive of motor vehicles in
general such as passenger automobiles including sports utility
vehicles (SUV), buses, trucks, various commercial vehicles,
watercraft including a variety of boats and ships, aircraft, and
the like, and includes hybrid vehicles, electric vehicles, plug-in
hybrid electric vehicles, hydrogen-powered vehicles and other
alternative fuel vehicles (e.g. fuels derived from resources other
than petroleum).
[0017] As referred to herein, a hybrid vehicle is a vehicle that
has two or more sources of power, for example both gasoline-powered
and electric-powered.
[0018] The above features and advantages of the present invention
will be apparent from or are set forth in more detail in the
accompanying drawings, which are incorporated in and form a part of
this specification, and the following Detailed Description, which
together serve to explain by way of example the principles of the
present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The above and other objects, features and advantages of the
present invention will become apparent from the following
description of preferred embodiments given in conjunction with the
accompanying drawings, in which:
[0020] FIG. 1 schematically illustrates formation of .pi.-.pi.
interaction between 1-pyrenecarboxylic acid (1-PCA) and the surface
of crystalline carbon;
[0021] FIG. 2 shows a result of water dispersibility test for
measuring hydrophilic property of carbon nanofiber (CNF) (a) and
1-PCA treated CNF (b);
[0022] FIG. 3 shows a result of water dispersibility test for
measuring hydrophilic property of 1-PCA treated carbon nanocage
(CNC) (a) and 1-aminopyrene (1-AP) treated CNC (b);
[0023] FIG. 4 shows high resolution transmission electron
microscopy (HR-TEM) images of catalysts prepared by supporting
platinum (Pt) on a herringbone CNF support treated or untreated
with 1-PCA (magnification: 200,000.times.);
[0024] FIG. 5 shows HR-TEM images of catalysts prepared by
supporting Pt on a platelet CNF support treated or untreated with
1-PCA (50,000.times.);
[0025] FIG. 6 shows HR-TEM images of Pt/CNC (a), 1-AP treated
Pt/CNC (b) and 1-PCA treated Pt/CNC (c) (200,000.times.);
[0026] FIG. 7 shows X-ray diffraction patterns of catalysts
prepared by supporting Pt on a herringbone CNF support treated or
untreated with 1-PCA;
[0027] FIG. 8 shows performance of unit cells of catalysts prepared
by supporting Pt on a herringbone CNF support treated or untreated
with 1-PCA under air condition;
[0028] FIG. 9 shows performance of membrane electrode assemblies
(MEAs) of catalysts prepared by supporting Pt on an untreated
herringbone CNF support (a) or on a 1-PCA treated herringbone CNF
support (b) under oxygen condition, before and after corrosion;
and
[0029] FIG. 10 shows generation of CO.sub.2 resulting from
corrosion of catalysts prepared by supporting Pt on a herringbone
CNF support treated or untreated with 1-PCA.
[0030] It should be understood that the appended drawings are not
necessarily to scale, presenting a somewhat simplified
representation of various preferred features illustrative of the
basic principles of the invention. The specific design features of
the present invention as disclosed herein, including, for example,
specific dimensions, orientations, locations, and shapes will be
determined in part by the particular intended application and use
environment.
DESCRIPTION OF SPECIFIC EMBODIMENTS
[0031] As described herein, the present invention includes a method
for increasing the hydrophilic properties of crystalline carbon
using a surface modifier.
[0032] In one embodiment, .pi.-.pi. interaction is formed between
the surface modifier and the crystalline carbon and hydrophilic
properties are provided by a hydrophilic functional group of the
surface modifier.
[0033] In another embodiment, the surface modifier is one selected
from 1-pyrenecarboxylic acid, 9-anthracenecarboxylic acid,
fluorene-1-carboxylic acid, 1-pyrenebutyric acid, naphthoic acid,
1-pyreneacetic acid, naphtho-2-aminopyridine-3-carboxylic acid,
1,4-benzodioxane-6-carboxylic acid, 2-mercaptobenzimidazole,
2-naphthalenethiol, 1-mercaptopyrene, 6-mercaptobenzopyrene and
1,4-benzenedithiol.
[0034] In another further embodiment, the crystalline carbon is one
selected from carbon nanotube, carbon nanofiber, carbon nanocoil
and carbon nanocage.
[0035] In another aspect, the present invention features a method
for preparing a Pt/C catalyst, comprising increasing hydrophilic
property of crystalline carbon using a surface modifier; supporting
platinum (Pt) on the crystalline carbon to prepare a catalyst; and
washing and drying thus prepared catalyst to remove unwanted
organic materials.
[0036] In another embodiment, the present invention features a Pt/C
catalyst prepared by a method described in any one of the
above-mentioned aspects herein.
[0037] In another further embodiment, the present invention
features a fuel cell electrode comprising the catalyst according to
a method described in any one of the above-mentioned aspects
herein.
[0038] In still another embodiment, the present invention features
a fuel cell comprising the electrode according to a method
described in any one of the above-mentioned aspects herein.
[0039] Certain advantages, features and aspects of the present
invention will become apparent from the following description of
the embodiments with reference to the accompanying drawings, which
is set forth hereinafter.
[0040] In certain preferred embodiments, the present invention
provides a method for increasing hydrophilic property of
crystalline carbon using a surface modifier.
[0041] In preferred embodiments, the crystalline carbon may include
carbon nanotube (CNT), carbon nanofiber (CNF), carbon nanocoil,
carbon nanocage (CNC), etc. Preferably, the aforementioned tend to
agglomerate in a polar solvent because of water repellency.
Preferably, to address the issue of water repellency, hydrophilic
property of the surface of the crystalline carbon may be suitably
increased by forming .pi.-.pi. interaction between the aromatic
surface of the crystalline carbon and a surface modifier having an
hydrophilic functional group such as carboxyl (--COOH) or thiol
(--SH). In certain preferred embodiments, the surface modifier may
be an aromatic cyclic compound having a carboxyl or thiol group,
such as, but not limited to, 1-pyrenecarboxylic acid (1-PCA),
9-anthracenecarboxylic acid, fluorene-1-carboxylic acid,
1-pyrenebutyric acid, naphthoic acid, 1-pyreneacetic acid,
naphtho-2-aminopyridine-3-carboxylic acid,
1,4-benzodioxane-6-carboxylic acid, 2-mercaptobenzimidazole,
2-naphthalenethiol, 1-mercaptopyrene, 6-mercaptobenzopyrene and
1,4-benzenedithiol. Preferably, one selected from 1-PCA,
9-anthracenecarboxylic acid, fluorene-1-carboxylic acid,
1-pyrenebutyric acid, naphthoic acid, 2-mercaptobenzimidazole and
2-naphthalenethiol is used. More preferably, 1-PCA, which is
represented by Chemical Formula 1, shown below, is used.
##STR00001##
[0042] In exemplary preferred embodiments, the crystalline carbon
and the surface modifier are stirred in an ethanol solvent.
Preferably, the crystalline carbon is recovered using a filtering
apparatus and suitably dried to obtain crystalline carbon with
increased hydrophilic property.
[0043] In certain preferred embodiments, the present invention also
provides a method for preparing a Pt/C catalyst, comprising:
increasing hydrophilic property of crystalline carbon by suitably
treating the surface of the crystalline carbon with a surface
modifier; supporting platinum (Pt) on the crystalline carbon; and
washing and drying thus prepared catalyst.
[0044] Preferably, the procedure of increasing hydrophilic property
of the crystalline carbon using the surface modifier is the same as
described above.
[0045] According to further preferred embodiments of the present
invention, polyol process is employed to suitably prepare the
catalyst by supporting Pt on the crystalline carbon. Preferably, in
the polyol process, ethylene glycol is used at once as a solvent
and as a reducing agent. Preferably, glycolate anion produced as
ethylene glycol is oxidized, acts as a stabilizer, and maintains Pt
particles at nano size. In further preferred embodiments, sodium
hydroxide is added to ethylene glycol to keep pH at 12 or higher.
In further preferred embodiments, an adequate amount of Pt
precursor is added to a solvent and stirred. Preferably, the Pt
precursor may be platinum chloride, potassium tetrachloroplatinate,
tetraammineplatinum chloride, etc. In further preferred
embodiments, after the crystalline carbon treated with the surface
modifier is added to the solvent, the temperature is raised to
160.degree. C. while sufficiently stirring. Preferably, during this
procedure, the Pt precursor is suitably reduced as ethylene glycol
is oxidized. Preferably, the glycolate anion produced as ethylene
glycol is oxidized and prevents agglomeration of the reduced Pt
particles. In further preferred embodiments, after the reaction is
suitably completed, the temperature is decreased to room
temperature and the solution is sufficiently stirred.
[0046] Preferably, thus prepared catalyst is suitably washed and
dried to remove unwanted organic materials. Preferably, during this
procedure, organic acids and other impurities produced during
oxidation of ethylene glycol are suitably removed by sufficiently
washing with ultrapure water and drying. As a result, the Pt/C
catalyst is obtained as powder.
[0047] In accordance with preferred methods for preparing a Pt/C
catalyst of the present invention as described herein, hydrophilic
property of the crystalline carbon is suitably increased by forming
.pi.-.pi. interaction between the surface of the crystalline carbon
and the surface modifier. Accordingly, a high-content, highly
dispersed, highly durable Pt nanocatalyst resistant to
electrochemical corrosion may be suitably prepared. Preferably,
when used for an electrode of a fuel cell, the amount of the
catalyst suitably coated on the electrode may be decreased.
Accordingly, the electrode becomes thinner and has improved fuel
transfer efficiency.
EXAMPLES
[0048] The examples and experiments according to certain preferred
embodiments of the present invention are now be described. The
following examples are for illustrative purposes only and not
intended to limit the scope of the present invention.
Example 1
[0049] In a first example, 1-Pyrenecarboxylic acid (1-PCA, 100 mg)
was added to ethanol (400 mL) and stirred for 30 minutes. Then,
herringbone carbon nanofiber (CNF, 200 mg) was added to the 1-PCA
solution and stirred for 6 hours. This is to form .pi.-.pi.
interaction between the pyrene of 1-PCA and the graphene of CNF.
1-PCA treated CNF was suitably recovered by filtration under
reduced pressure and dried in an oven at 40.degree. C. for 30
minutes. 1-PCA treated CNF (144 mg) was added to ethylene glycol
(25 mL) and stirred for 20 minutes. Then, to prepare a 40 wt %
Pt/CNF catalyst, after adding 0.1 M sodium hydroxide (NaOH)
solution (100 mL) and a Pt precursor PtCl.sub.4 (150 mg), the
mixture was stirred for 30 minutes. After carrying out a reaction
at 160.degree. C. for 3 hours under reflux to reduce the Pt
precursor, the mixture was suitably cooled to room temperature and
adjusted to pH 3 using sulfuric acid (H.sub.2SO.sub.4). Then, after
exposing to air, the mixture was stirred for 12 hours. The reaction
solution was filtered under reduced pressure to recover the
prepared catalyst, which was washed several times with ultrapure
water and dried in an oven at 160.degree. C. for 30 minutes. As a
result, the 1-PCA treated Pt/CNF catalyst was obtained.
Example 2
[0050] In a second example, a catalyst was prepared in the same
manner as Example 1, except for using platelet CNF instead of
herringbone CNF.
Example 3
[0051] In a third example, a catalyst was prepared in the same
manner as Example 1, except for using carbon nanocage (CNC) instead
of CNF.
Comparative Example 1
[0052] Untreated Pt/CNF was prepared in the same manner as Example
1 by a polyol process without surface modification of CNF.
Comparative Example 2
[0053] Untreated Pt/CNF was prepared in the same manner as Example
2 by a polyol process without surface modification of CNF.
Comparative Example 3
[0054] Untreated Pt/CNC was prepared in the same manner as Example
3 by a polyol process without surface modification of CNC.
Comparative Example 4
[0055] A catalyst was prepared in the same manner as Example 3,
using 1-aminopyrene (1-AP) for surface modification of CNC.
Test Example 1
Testing of Increased Hydrophilic Property of 1-PCA Treated
Crystalline Carbon
[0056] In order to test increased hydrophilic property of 1-PCA
treated CNF prepared in Example 1, water dispersibility test was
carried out. Untreated CNF was also tested for comparison. The
results are shown in FIG. 2. After mixing CNF with water and then
adding hexane, it was observed whether CNF was dispersed in the
aqueous layer. As shown in FIG. 2, 1-PCA treated CNF (b) was
dispersed well in water, differently from untreated CNF (a). This
demonstrates that 1-PCA increases hydrophilic property of CNF.
[0057] Also, water dispersibility test was carried out to test
hydrophilic property of 1-PCA treated CNC (a) prepared in Example 3
and 1-AP treated CNC (b) prepared in Comparative Example 4. The
results are shown in FIG. 3. When CNC with high water repellency
was treated with 1-PCA or 1-AP, CNC was dispersed well in the
aqueous layer because of increased hydrophilic property. However, 6
hours later, 1-AP treated CNC (b) moved to the hexane layer whereas
1-PCA treated CNC (a) remained in the aqueous layer. This result
shows that 1-PCA treated CNC has higher hydrophilic property than
1-AP treated CNC.
Test Example 2
Testing of Particle Size and Dispersion of Supported Pt
[0058] Dispersion of Pt on the Pt/C catalysts prepared in Examples
1 to 3 and Comparative Examples 1 to 4 was tested by high
resolution transmission electron microscopy (HR-TEM).
[0059] FIG. 4 (a) is an HR-TEM image of the catalyst prepared in
Comparative Example 1. Pt particle size was 2.5 nm. FIG. 4 (b) is
an HR-TEM image of the catalyst prepared in Example 1. Pt particle
size was 2.5 nm. There was no difference in particle size. However,
the catalyst treated with 1-PCA (FIG. 4 (b)) showed higher Pt
density and better dispersion than FIG. 4 (a). It is because the
carboxyl (--COOH) group of 1-PCA not only increases hydrophilic
property of carbon but also acts as a conglutination site of Pt
thereby leading to uniform supporting of Pt and increased
supporting density thereof.
[0060] FIG. 5 (a) shows an HR-TEM image of the catalyst prepared in
Comparative Example 2 and FIG. 5 (b) shows an HR-TEM image of the
catalyst prepared in Example 2 (50,000.times.). In FIG. 5 (a),
regions where Pt is not supported or Pt particles are agglomerated
are observed. The 1-PCA treated catalyst (FIG. 5(b)) showed higher
Pt density and better dispersion than FIG. 5(a). It is because the
1-PCA CNF has increased hydrophilic property while supporting of Pt
on the 1-PCA untreated CNF is difficult because of water
repellency.
[0061] FIG. 6 shows HR-TEM images of the catalysts prepared in
Comparative Example 3 (a), Comparative Example 4 (b) and Example 1
(c). The catalyst with water repellency (a) shows regions where Pt
is not supported or Pt particles are agglomerated. The 1-AP treated
catalyst (b) shows more uniform supporting of Pt than (a) but with
increased Pt particle size. The 1-PCA treated catalyst (c) shows
improved dispersion as (b) as well as small Pt particle size as
(a).
[0062] FIG. 7 shows X-ray diffraction patterns of the catalysts
prepared in Comparative Example 1 and Example 1. Pt particle size
was calculated using the Scherrer formula from the Pt (220) peak at
2.theta.=67.degree.. Pt particle size was 2.0 nm for Comparative
Example 1 and 1.8 nm for Example 1. Accordingly, it can be seen
that Pt particle size was 0.2 nm smaller when 1-PCA treated CNF was
used as the support.
[0063] Further, Pt particle size of the catalysts prepared in
Comparative Examples 3 and 4 and Example 3 was calculated as 2.5
nm, 2.7 nm and 2.5 nm, respectively.
[0064] Accordingly, when compared with treatment with 1-AP, the
treatment with 1-PCA enables easier improvement hydrophilic
property of the water-repellent support and preparation of a
high-content, highly dispersed Pt/C catalyst.
Test Example 3
Measurement of Pt Supporting Ratio and Catalytic Active Area
[0065] Inductively coupled plasma (ICP) and cyclic voltammetry (CV)
experiments were performed to measure Pt supporting ratio and
catalytic active area of the catalysts. Pt supporting ratio
measured by ICP analysis was 23.9 wt % for Comparative Example 1
and 35.5 wt % for Example 1, 60% and 89% of the target value 40 wt
%, respectively. Effective catalytic active area of the Pt catalyst
measured by CV experiment was 50.3 m.sup.2/g Pt and 51.2 m.sup.2/g
Pt, respectively. The catalytic active area was similar without
regard to the 1-PCA treatment. This is because, as seen from the
X-ray diffraction patterns and the HR-TEM images, the particle size
of Pt supported on CNF differs only by 0.2 nm.
[0066] Comparative Examples 3 and 4 and Example 3 showed Pt
supporting ratio of 35.0 wt %, 36.0 wt % and 40 wt %,
respectively.
Test Example 4
Measurement of Performance of Unit Cell Under Air Condition
[0067] A fuel cell electrode was prepared using the catalyst
prepared in Example 1 or Comparative Example 1 and performance of
the unit cell was measured under air condition. The result is shown
in FIG. 8. 1.5 stoic hydrogen was supplied to the anode, and 2
stoic air was supplied to the cathode. 1-PCA treatment (Example 1)
resulted in better performance of 0.89 A/cm.sup.2 at 0.6 V than
0.78 A/cm.sup.2 of Comparative Example 1 under air condition,
whereas similar performance was observed without regard to 1-PCA
treatment under oxygen condition. This is because Pt supporting
ratio of Example 1 (35.5 wt %), wherein the catalyst was treated
with 1-PCA without growth of Pt particles, is higher than that of
Comparative Example 1 (23.9 wt %), and, thus, the amount of the
catalyst coated on the electrode decreases. Decreased coating
amount of the catalyst on the electrode results in smaller
electrode thickness and improved fuel transfer. As a result, the
performance under air condition is improved.
Test Example 5
Catalyst Corrosion Test
[0068] Corrosion test was performed on the catalysts prepared in
Example 1 and Comparative Example 1. Commercially available Johnson
Matthey 40 wt % Pt/C catalyst was mixed with 5 wt % Nafion solution
and coated on the anode side of N212 Nafion membrane at Pt 0.4
mg/cm.sup.2. On the cathode side of the N212 Nafion membrane, the
catalyst prepared in Comparative Example 1 was mixed with 5 wt %
Nafion solution and coated at Pt 0.4 mg/cm.sup.2. Then, after
connecting a gas diffusion layer (GDL) and a gasket to the unit
cell, corrosion test was carried out. Before starting corrosion,
measurement of performance of the membrane-electrode assembly (MEA)
under oxygen condition, impedance and CV was carried out. Then, a
constant voltage of 1.4 V.sub.SHE was supplied to the cathode for
30 minutes using a potentiostat to corrode the catalyst layer. The
counter electrode and the reference electrode of the potentiostat
were connected to the anode of the unit cell and the working
electrode was connected to the cathode. Hydrogen was supplied to
the anode at 20 mL/min and nitrogen was supplied to the cathode at
30 mL/min. The unit cell was maintained at 90.degree. C. CO.sub.2
resulting from the corrosion of the catalyst layer was measured in
real time using a mass spectrometer. Upon completion of the
corrosion, performance of the MEA, impedance and CV were measured
to compare them with those before the corrosion. Based on the
results, corrosion resistance of the catalyst was evaluated.
[0069] FIG. 9 and FIG. 10 show the corrosion test result of the
catalysts prepared in Example 1 and Comparative Example 1. The
result is summarized in Table 1, shown below.
TABLE-US-00001 TABLE 1 Performance of Active surface area MEA
(A/cm.sup.2) (m.sup.2/g) Impedance (O cm.sup.2) CO.sub.2 Before
After Before After Before After production corrosion corrosion
corrosion corrosion corrosion corrosion (.mu.L) Comp. 1.66 1.50
32.5 31.7 0.0429 0.0458 18 .mu.L Ex. 1 -9.6% -2.5% +6.8% Ex. 1 1.67
1.51 30.1 28.8 0.0394 0.0403 19 .mu.L -9.6% -4.3% +2.3%
[0070] Unit cell performance under oxygen condition at 0.6 V before
corrosion was 1.66 A/cm.sup.2 for Comparative Example 1 and 1.67
A/cm.sup.2 for Example 1. After corrosion of the cathode catalyst
by supplying a voltage of 1.4 V.sub.SHE to the cathode, unit cell
performance at 0.6 V decreased by 9.6% for Comparative Example 1
(FIG. 9 (a)) and also by 9.6% for Example 1 (FIG. 9(b)). Active
surface area decreased by 2.5% for Comparative Example 1 and by
4.3% for Example 1. Impedance increased by 6.8% for Comparative
Example 1 and by 2.3% for Example 1. FIG. 10 shows a result of
measuring generation of CO.sub.2 resulting from corrosion of the
Pt/C catalysts using a mass spectrometer. As shown in FIG. 10,
there was no big difference between Comparative Example 1 (18
.mu.L) and Example 1 (19 .mu.L). These results show that the
formation of .pi.-.pi. interaction on crystalline carbon using
1-PCA followed by the supporting of Pt has no significant effect on
electrochemical corrosion.
[0071] While the present invention has been described with respect
to the specific embodiments, it will be apparent to those skilled
in the art that various changes and modifications may be made
without departing from the spirit and scope of the invention as
defined in the following claims.
* * * * *